Insights into the Electrocatalytic Hydrogen Evolution Reaction Mechanism on Two-Dimensional Transition-Metal Carbonitrides (MXene)
Insights into the Electrocatalytic Hydrogen Evolution Reaction Mechanism on Two-Dimensional Transition-Metal Carbonitrides (MXene)
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二维过渡金属碳氮化物（MXene）电催化析氢反应机理的见解
DOI：
10.1002/chem.201804686
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发表时间：
2018-12-10
影响因子：
4.3
通讯作者：
Li, Neng
中科院分区：
文献类型：
--
作者：
Huang, Bin;Zhou, Naigen;Li, Neng
开发高活性的非贵金属H-2析氢催化剂是电催化和光催化生产H-2领域的一大挑战。在这项工作中，使用定义良好的密度泛函理论（DFT）计算研究了高质量的过渡金属碳氮化物M3CN （MXene）。系统地研究了裸M3CNO2、表面修饰M3CNO2和过渡金属修饰M3CNO2的结构构型、H吸附自由能（δ G(H)）和电荷转移。计算结果表明，所有过渡金属碳氮化物均表现出H原子与催化剂的强结合。此外，根据G(H)的结果，只有Ti3CNO2和Nb3CNO2具有成为HER活性催化剂的潜力。为了克服HER活性差的限制，我们在Ti3CNO2表面应用O和OH混合基团以及TMs修饰来调节HER活性，并观察到HER活性的显着提高。总的来说，这项工作对过渡金属碳氮化物（MXene）进行了深入的研究，并开辟了坚固的金属碳氮化物作为高效、低成本的MXene基纳米复合材料的无贵金属助催化剂的新设计。
Developing highly active, non-noble-metal H-2-evolution catalysts is appealing yet still remains a great challenge in the field of electrocatalytic and photocatalytic H-2 production. In this work, high quality transition-metal carbonitrides M3CN (MXene) are investigated using well-defined density functional theory (DFT) calculations. The structural configurations, H-adsorption free energy (Delta G(H)) and charge transfer for bare, surface-terminated and transition-metal (TM)-modified M3CNO2 are systematically studied. The calculated results indicate that all bare transition metal carbonitrides exhibit strong binding between H atom and catalysts. In addition, only Ti3CNO2 and Nb3CNO2 have the potential to be HER active catalysts based on the Delta G(H) results. In an attempt to overcome poor HER activity limitations, we apply O as well as OH mixed groups and TMs modification on the Ti3CNO2 surface for tuning HER activity, and a significant improvement of HER activity is observed. Overall, this work presents in-depth investigations for transition-metal carbonitrides (MXene) and opens up new designs for robust metal carbonitrides as noble-metal-free cocatalysts for highly efficient and low-cost MXene-based nanocomposites for water splitting applications.